CN103483135A - Preparation method of high-purity ethylidene norbornene (ENB) - Google Patents
Preparation method of high-purity ethylidene norbornene (ENB) Download PDFInfo
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- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000007670 refining Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 59
- 238000010992 reflux Methods 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 39
- 239000000470 constituent Substances 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 238000000605 extraction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 21
- 238000005336 cracking Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- -1 methyl ethyl Chemical group 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 2
- UHZLTTPUIQXNPO-UHFFFAOYSA-N 2,6-ditert-butyl-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C UHZLTTPUIQXNPO-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 34
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 24
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 125000002619 bicyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 12
- 238000005755 formation reaction Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 238000010606 normalization Methods 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 7
- 238000006471 dimerization reaction Methods 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001020 rhythmical effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical class C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RCQKOGBSRYPVJF-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-1-ene Chemical group C1CC2=CCC1(C=C)C2 RCQKOGBSRYPVJF-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of high-purity ethylidene norbornene (ENB), which comprises the following steps: 1) preparing cyclopentadiene (CPD) from cracked C9 bicyclic section distillate; 2) reacting the CPD and 1,3-butadiene (BD) in a non-dead-volume cascade tubular reactor to generate 5-vinyl-2-norbornene (VNB); 3) separating the crude VNB to obtain refined VNB, collecting the unreacted BD, CPD and circulating solvent, and returning to the front of the tubular reactor, thereby forming a circulating loop; and 4) dehydrating the refined VNB obtained in the step 3), carrying out isomerization reaction to obtain crude ENB, and removing light and heavy components from the crude ENB by a refining tower to obtain the high-purity ENB. The method has the advantages of simple and reliable process route and low facility request, and is suitable for large-scale production.
Description
Technical field
The invention belongs to the ethylidene norbornene preparation field, particularly a kind of preparation method of high purity ethylidene norbornene.
Background technology
Ethylidene norbornene can be produced ethylene-propylene rubber(EPR) with ethene, copolymerization of propylene, but its 3rd monomer as ethylene-propylene rubber(EPR) is not only given the cure of ethylene-propylene rubber(EPR), and has that reactive behavior is large, vulcanization rate is fast, secondary reaction is little.Resulting ethylene-propylene rubber(EPR) also has the performances such as anti-electric discharge, water-fast steam, anti-ozone, chemical-resistant resistance (solvent, acid, alkali etc.), can be used for the material modified of the material of construction such as rubber item around engine, water board and rubber-resin blend.Because of ethylidene norbornene as the 3rd monomer of ethylene-propylene rubber(EPR) by above-mentioned advantage, make its rate of selecting of the 3rd monomer in the ethylene-propylene rubber(EPR) industry account for greatly 85%.Ethylidene norbornene is to generate 5-vinyl-2-norbornylene by cyclopentadiene and 1,3-butadiene by Diels-Alder reaction, through isomerization reaction, is obtaining ethylidene norbornene.But cyclopentadiene and 1 in reaction process, side reaction can occur in the 3-divinyl, generate tetrahydroindene, 4-vinyl-1-norbornylene, dicyclopentadiene and polymer etc., the generation of side reaction will reduce selectivity and the yield of principal product, and its main reaction equation and side reaction equation are as follows:
Main reaction:
Side reaction:
At Chinese patent CN1580015A, a kind of generation method of ethylidene norbornene intermediate is disclosed.This patent has just been described the synthetic method of ethylidene norbornene intermediate 5-vinyl-2-norbornylene, and preparation, continuous tubular reactor device structure and the control program and the 5-vinyl-2-norbornylene isomerization that do not relate to cyclopentadiene generate ethylidene norbornene.The method is raw material cyclopentadiene, divinyl, solvent and stopper to be joined to reactor carry out rhythmic reaction, and in rhythmic reaction, the concentration of reactant can present graded, will cause the selectivity of 5-vinyl-2-norbornylene and turnover ratio to reduce.
At U.S. Pat 4777309, US4538013, a kind of synthetic method for the preparation of ENB intermediate 5-vinyl-2-norbornylene is disclosed.The method is not mentioned preparation method and continuous tubular reactor device structure and the control program of CPD.
Disclose a kind of preparation method of inferior vinyl norbornene in Chinese patent CN102123973A, this patent, described DCPD cracking in the inertia heat transfer fluid and obtained CPD, reacts with divinyl and produce VNB, VNB carried out to isomerization reaction generation ENB.But the method is not mentioned the purification process of VNB, and relevant process control condition.
Disclose a kind of crude product dicyclopentadiene and the divinyl reaction pure dicyclopentadiene of preparation and ethylidene norbornene used in Chinese patent CN1377869A, the method is mentioned DCPD and THI purification step, by rectifying, DCPD and THI is divided out.But the method does not have dimerization mode and the process control of detailed statement VNB.
The preparation method of disclosed vinyl norbornene and intermediate thereof in above-mentioned patent, all there is no the dimerization mode of VNB in the preparation process of the whole vinyl norbornene of detailed statement and the refining mode of ENB, do not mention the mode of utilizing of all the other by products in production process yet.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of high purity ethylidene norbornene, and the method operational path is simple and reliable, not high to equipment requirements, is applicable to large-scale production.
The preparation method of a kind of high purity ethylidene norbornene of the present invention comprises:
(1) cracking carbon nine dicyclo section fractions are after the depolymerization of depolymerization still, and the thick CPD obtained sends into the CPD treating tower, and the depolymerization stillage residue is sent into the hot polymerization resin device by transferpump, and tower top obtains high-purity C PD, and at the bottom of tower, raw material returns to the depolymerization still; Wherein, the depolymerization temperature is 170～250 ℃, and operating pressure is 0.03～0.3MPa (G), and the residence time is 1.5～3h; The treating tower tower top temperature is 40～60 ℃, and the tower reactor temperature is 140～170 ℃, and working pressure is 0.03～0.3MPa (G), and reflux ratio is 0.5～4;
(2) above-mentioned high-purity C PD and circulating solvent, polymerization retarder are mixed on pipeline after and 1,3-butadiene prepared burden, the mass ratio of CPD, BD and circulating solvent is 1:1:1,100～2000ppm that the consumption of polymerization retarder is reactant; Through line mixer, fully mix, after kick off temperature by cooling heater heats to 80～120 ℃, be transported to the series connection tubular reactor and carry out Diels-Alder reaction, after temperature of reaction rises, by water cooler, lower the temperature, be transported to again the series connection tubular reactor and carry out Diels-Alder reaction, the Diels-Alder reaction service temperature is 120～180 ℃, working pressure is 1～5MPa (G), the residence time is 60～240min, and the reaction mixture of generation is from the bottom discharge of reactor;
(3) reaction mixture obtained above enters rectifying tower (T2) after water cooler (E3) is cooling, the tower top service temperature is 0～20 ℃, operating pressure is 0.1～0.3MPa, tower top obtains unreacted 1, turn back to series connection tubular reactor (R2) after the 3-divinyl is freezing front, material by transferpump (P3) extraction at the bottom of tower enters rectifying tower (T3), the tower top service temperature is 30～70 ℃, working pressure is 0.1～0.5MPa, reflux ratio is 0.5～2, tower top obtains unreacted CPD and circulating solvent, and to turn back to series connection tubular reactor (R2) front, obtain crude ethylene basic ring hexene VCH at the bottom of tower,
(4) the thick VCH obtained at the bottom of above-mentioned tower enters rectifying tower (T4), and the tower top service temperature is 30～70 ℃, and working pressure is 0.001～0.005MPa, and reflux ratio is 0.5～3, and tower top obtains refining VCH, obtains mixture at the bottom of tower;
(5) mixture obtained at the bottom of step (4) tower enters rectifying tower (T5), and the tower top service temperature is 30～80 ℃, and working pressure is 0.001～0.005MPa, and reflux ratio is 0.5～3, and tower top obtains VNB, obtains mixture at the bottom of tower;
(6) VNB that step (5) tower top obtains is after molecular sieve drying bed (R6) dehydration, send into isomerization reactor (R7), under the effect of isomerization catalyst, reaction generates thick ENB, the isomerization reaction service temperature is 10～30 ℃, working pressure is 0.01～0.2MPa, and the residence time is 3～7h; The mixture obtained at the bottom of tower enters rectifying tower (T6), and the tower top service temperature is at 40～90 ℃, and working pressure is 0.001～0.005MPa, reflux ratio 0.5～3, and tower top obtains tetrahydroindene THI, obtains the DCPD fraction at the bottom of tower;
(7) thick ENB step (6) obtained enters the ENB rectifying tower, operating pressure is 0.001～0.01MPa (A), the tower top service temperature is 50～60 ℃, the side line service temperature is 60～80 ℃, the tower reactor service temperature is 70～90 ℃, side line obtains highly purified ENB, obtains light constituent at the bottom of tower, obtains heavy constituent at the bottom of tower.
High-purity C PD mass content in described step (1) >=99%; The depolymerization temperature is 220～250 ℃, and operating pressure is 0.05～0.1Mpa (G); Tower top temperature is 40～50 ℃, and the tower reactor temperature is 140～160 ℃, and reflux ratio is 2～4.
In described step (2), high-purity C PD adopts refrigerated water to carry out cold insulation before mixing with circulating solvent, polymerization retarder.
Circulating solvent in described step (2) can be taken from aromatic hydrocarbons, alkanes, cycloalkane and monobasic lipid etc., is methylcyclopentane, octane-iso, 6# solvent oil, THF, heptane, methyl ethyl ester or vinyl acetic monomer; Polymerization retarder is compound inhibitor, and by 2,6 di t butyl phenol, 2,6-di-tertiary butyl methyl phenol and naphthyl alcohol 2:1:1 in mass ratio are composited.
Diels-Alder reaction service temperature in described step (2) is 120～140 ℃, and working pressure is 3～5MPa (G), and the residence time is 180～240min.
Rectifying tower tower top service temperature in described step (3) is 10～20 ℃, and working pressure is 0.2～0.3MPa (G); Rectifying tower (T3) tower top service temperature is 40～60 ℃, and working pressure is 0.1～0.2MPa (G), and reflux ratio is 1～2.
Rectifying tower tower top service temperature in described step (4) is 40～60 ℃, and working pressure is 0.003～0.005MPa (A), and reflux ratio is 1～2; Rectifying tower tower top service temperature in described step (5) is 50～70 ℃, and working pressure is 0.003～0.005MPa (A), and reflux ratio is 1～2.
Super basic catalyst (the Na that isomerization catalyst in described step (6) is pH>=43
2o-NaOH)/AL
2o
3; The isomerization reaction service temperature is 20～30 ℃, and working pressure is 0.05～0.1MPa (G), and the residence time is 5～6h; Rectifying tower tower top service temperature is 50～70 ℃, and working pressure is 0.003～0.005MPa (A).
ENB rectifying tower system working pressure in described step (7) is 0.003～0.005MPa (A); The purity of side line extraction ENB >=99%.
The ENB light constituent that the THI that the VCH that described step (4) obtains and step (6) obtain, step (7) obtain (for the non-aromatics ring compound) is at BF
3effect under, at-20～120 ℃ of polymerization reaction take places, generate copolymerized petroleum resin with sylvic oil, the main component of this copolymerized petroleum resin comprises Vinyl toluene, indenes and first indenes, has advantages of that softening temperature is low, narrow molecular weight distribution, consistency; The ENB heavy constituent that the DCPD cut that the depolymerization stillage residue that described step (1) obtains and step (6) obtain, step (7) obtain, carry out heat polymerization under 200～300 ℃, generate the hot polymerization petroleum resin, have advantages of that sulphur content is low, look is number low, smell is little.
Operational path of the present invention generates without final by product.
Exist the dimer of a large amount of dicyclopentadiene, cyclopentadiene and methyl cycle pentadiene dimer, cyclopentadiene and styrenic in the middle of the nine dicyclo section fraction last running of cracking of ethylene carbon, the present invention is usingd cracking of ethylene carbon nine dicyclo section fractions as the raw material for preparing CPD, can take full advantage of its DCPD component, improved the yield of CPD, overcome a large amount of losses of raw material when DCPD is the raw material depolymerization, and reduced raw materials cost.
The present invention adopts refrigerated water to carry out cold insulation at CPD, can be in CPD and 1, the generation of the minimizing CPD dimerization reaction of trying one's best before the 3-divinyl, adopt level Four series connection shell and tube reactor, from reactor bottom charging top discharge, dimerization reaction is carried out under the condition without dead volume, by centre, water cooler being set, remove reaction heat.Improved the selectivity of 1,3-butadiene, the yield of intermediate product VNB is improved.
The present invention, before VNB advances isomerization reactor, is provided with the molecular sieve drying bed, has removed the moisture in VNB, has played guard catalyst, improves the catalyzer effect in work-ing life.
The thick ENB of the present invention after to isomerization made with extra care, and the high purity ENB content of side line extraction can reach more than 99%.
The copolymerized petroleum resin that by product THI, VCH in the present invention etc. adopt copolymerization process to produce, there is the advantages such as look is number shallow, narrow molecular weight distribution, DCPD fraction, depolymerization restructuring grade and adopt hot polymerization technique, produce the hot polymerization petroleum resin, this operational path no coupling product is generated, improved the comprehensive utilization ratio of raw material.
beneficial effect
(1) the present invention is a kind of technique syntheti c route of complete ethylidene norbornene, has comprised the mode of utilizing of its by product; The method is simple to operate, and to take cracking carbon nine dicyclo section fractions be the depolymerization raw material, and cost is low, and less demanding to equipment is applicable to large-scale production;
(2) the technique syntheti c route of ethylidene norbornene in the present invention, have a by product few, ethylidene norbornene yield advantages of higher; (3) the present invention adopts the series connection tubular reactor, can effectively stop the generation of temperature runaway phenomenon in the Diels-Alder reaction process, makes this technique safety and reliability;
(4) in the present invention with by product THI and VCH, the copolymerized petroleum resin that modified resin oil is produced, the advantage such as have that softening temperature is moderate, narrow molecular weight distribution, consistency are good;
(5) in the present invention, the yield of cyclopentadiene is greater than 95%, and the cyclopentadiene transformation efficiency is greater than 90%, and the selectivity of ethylidene norbornene is greater than 65%, and the yield of ethylidene norbornene is greater than 60%, and the ethylidene norbornene purity of producing is greater than 99%.
The accompanying drawing explanation
Fig. 1 is device of the present invention and schema;
Wherein, R1 is depolymerizing reactor, and R2/3/4/5 is the shell and tube dipolymer reactor, R6 is the molecular sieve drying bed, and R7 is isomerization reactor, and T1 is the CPD treating tower, T2 is de-divinyl tower, T3 is the desolventizing tower, and T4 is de-VCH tower, and T5 is the VNB treating tower, T6 is weight-removing column, T7 is the ENB treating tower, and E1 is the outer circulation water cooler, and P1, P2, P3, P4, P5, P6, P7, P8, P9 are material-handling pump, F1～F24 is that material involved in the present invention: F1 is cracking carbon nine dicyclo section fractions, the gaseous phase materials that F2 is depolymerization reaction, F3 is circulating solvent, F4 is stopper, F5 is 1, the 3-butadiene hydrocarbon, mixture after the F6 dimerization reaction, F7 is for removing circulating solvent and unreacted CPD, mixture after BD, F8 is the mixture removed after VCH, F9 is the refining tower reactor mixture obtained after VNB, F10 is the VNB after refining, the mixture that F11 is VCH and THI, F12 is the DCPD cut, F13 is the ENB product, F14 is the depolymerization heavy constituent, F15 is CPD, circulating solvent and unreacted CPD that F16 returns for circulation, the mixture of BD, F17 is VCH, F18 is THI, F19 is copolymerized petroleum resin, F20 is the hot polymerization petroleum resin, F21 is heavy constituent, F22 is light constituent, F23 is for removing 1, mixture after the 3-divinyl, F24 for the circulation return 1, the 3-divinyl.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Following table 1 is that cracking of ethylene carbon nine main compound form
Table 1
The raw material extraction process:
Cracking of ethylene by-product C 9 fraction is under 10～25Kpa (A) at working pressure, obtains through underpressure distillation cutting component that boiling point is 165～200 ℃ and is the present invention and uses material carbon nine dicyclo section cuts.It forms in Table 2
The nine dicyclo section fractional compositions of table 2 cracking carbon
Sylvic oil forms in Table 3.
Table 3 sylvic oil forms
The technical process of various embodiments of the present invention as shown in Figure 1.
Embodiment 1
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, add again the polymerization retarder of 1000ppm, enter dipolymer reactor, by side cooler E2, control temperature at 130 ℃, 3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and high purity ENB product performance analytical results is in Table 4, and experimental result is in Table 5.
VNB and THI adopt BF3 as catalyzer and sylvic oil under 20 ℃ of conditions, carry out copolymerization, after question response 40min, add excessive NaOH to be neutralized, washed Removal of catalyst and NaOH with deionized water, material after Removal of catalyst and NaOH carries out flash distillation, removes unreacted solvent, obtains copolymerized petroleum resin.The gained copolymerized petroleum resin is measured by iron cobalt colorimetry, and look number is No. 3 looks, and softening temperature is 90 ℃.
DCPD cut and depolymerization stillage residue are at 250 ℃, 0.1MPa(G) operational condition under, the reaction 6h, the polymer fluid of production is removed rudimentary solvent by two-stage flash, obtain the hot polymerization petroleum resin, adopt iron cobalt colorimetry to be measured, look number is No. 11 looks, and softening temperature is 110 ℃.
Embodiment 2
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 2:1, mixed, mixed material mixes according to mass ratio 3:2 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 3
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1500ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 4
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 500ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 5
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:2, mixed, mixed material mixes according to mass ratio 3:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 6
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with methylcyclopentane, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 7
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with the 6# solvent oil, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 240min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 8
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 130 ℃ by side cooler E2,3MPa(G) the lower 160min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 9
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 150 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Embodiment 10
Cracking carbon nine dicyclo section fractions enter depolymerization still R1, in the depolymerization temperature, are 220 ℃, and operating pressure is 0.08MPa(G), the residence time is 1.5h; The F2 material generated enters CPD treating tower T1, the treating tower top is 40 ℃, the temperature of tower reactor is at 140 ℃, system pressure is 0.05MPa(G), reflux ratio is 2, high-purity CPD that tower top obtains, with octane-iso, according to mass ratio 1:1, mixed, mixed material mixes according to mass ratio 2:1 with BD, adding the polymerization retarder of 1000ppm, enter dipolymer reactor, control temperature at 170 ℃ by side cooler E2,3MPa(G) the lower 200min that stops, the formation reaction mixture is from the bottom discharge of dipolymer reactor R5.The mixture obtained enters rectifying tower T2 after water cooler E3 is cooling, and the tower top service temperature is at 10 ℃, and operating pressure is at 0.13MPa(G), before tower top obtains unreacted 1,3-butadiene and turns back to series connection tubular reactor R2 after freezing.Material by transferpump P3 extraction at the bottom of rectifying tower T2 tower enters rectifying tower T3, the tower top service temperature is at 35 ℃, and working pressure is 0.02MPa (G), and reflux ratio is 2, before tower top obtains unreacted CPD and circulating solvent and turns back to the Diels-Alder reaction device, obtain thick VCH at the bottom of tower.The thick VCH obtained at the bottom of tower enters rectifying tower T4, and the tower top service temperature is at 55 ℃, and working pressure is at 0.003MPa (A), and reflux ratio is 1, and tower top obtains refining VCH, obtains mixture at the bottom of tower.The mixture obtained at the bottom of tower advances rectifying tower T5, and the tower top service temperature is at 70 ℃, and working pressure is at 0.003MPa (A), reflux ratio 1, and tower top obtains VNB, obtains mixture at the bottom of tower.The VNB that tower top obtains is after be dewatered to<50ppm of molecular sieve drying bed R6, carry out isomerization reaction entering isomerization reactor R7, the isomerization reaction service temperature is 25 ℃, working pressure 0.05MPa (G), the residence time is 5h, the thick ENB obtained enters ENB treating tower T7, operating pressure is at 0.003MPa (A), the tower top service temperature is at 55 ℃, the side line service temperature is at 70 ℃, and the tower reactor service temperature is at 90 ℃, from the highly purified ENB of side line extraction, obtain light constituent at the bottom of tower, obtain heavy constituent at the bottom of tower.
Isomerization reactor R7 is 50L, and the isomerization catalyst loadings is 20kg.The ENB product obtained, the purity by gas-chromatography (area normalization method) to ENB is detected, and resulting ENB product purity can reach 99%, and experimental result is in Table 5.
Table 4: high purity ENB product performance table
| Project | Unit | Index |
| Purity | wt% | 99.42 |
| Water | wt%ppm | 50 |
| The end vinylic chemical compound | wt% | 0.12 |
| Vinyl?norbornene（VNB） | wt% | 0.13 |
| Light constituent C8/C9 | wt% | 0.08 |
| Heavy constituent | wt% | 0.15 |
| Colourity (APHA) | wt?ppm | 100 |
| Outward appearance | ? | Without particle or suspended particle |
Each embodiment result of table 5
| Title | CPD yield (%) | CPD turnover ratio (%) | VNB selection rate (%) | VNB yield (%) |
| Embodiment 1 | 95.12 | 92.53 | 66.01 | 61.08 |
| Embodiment 2 | 94.83 | 91.91 | 65.32 | 60.04 |
| Embodiment 3 | 95.14 | 92.28 | 66.32 | 61.20 |
| Embodiment 4 | 95.35 | 91.21 | 65.85 | 60.06 |
| Embodiment 5 | 95.54 | 92.31 | 66.45 | 61.34 |
| Embodiment 6 | 95.49 | 91.36 | 66.12 | 60.41 |
| Embodiment 7 | 95.12 | 92.13 | 66.41 | 61.18 |
| Embodiment 8 | 95.31 | 91.24 | 65.82 | 60.05 |
| Embodiment 9 | 95.22 | 91.58 | 65.95 | 60.40 |
| Embodiment 10 | 95.35 | 91.42 | 65.92 | 60.26 |
Claims (10)
1. the preparation method of a high purity ethylidene norbornene comprises:
(1) cracking carbon nine dicyclo section fractions are after depolymerization still (R1) depolymerization, the thick CPD obtained sends into CPD treating tower (T1), the depolymerization stillage residue is sent into the hot polymerization resin device by transferpump (P1), and tower top obtains high-purity C PD, and at the bottom of tower, raw material returns to depolymerization still (R1); Wherein, the depolymerization temperature is 170～250 ℃, and operating pressure is 0.03～0.3MPa, and the residence time is 1.5～3h; Treating tower (T1) tower top temperature is 40～60 ℃, and the tower reactor temperature is 140～170 ℃, and working pressure is 0.03～0.3MPa, and reflux ratio is 0.5～4;
(2) above-mentioned high-purity C PD and circulating solvent, polymerization retarder are mixed on pipeline after and BD prepared burden, the mass ratio of CPD, BD and circulating solvent is 1:1:1,100～2000ppm that the consumption of polymerization retarder is reactant, through line mixer (X1), fully mix, be heated to the kick off temperature of 80～120 ℃ by cooling well heater (E1) after, be transported to series connection tubular reactor (R2)/(R3) and carry out Diels-Alder reaction, after temperature of reaction rises, by water cooler (E2), lower the temperature, be transported to again series connection tubular reactor (R4)/(R5) and carry out Diels-Alder reaction, the Diels-Alder reaction service temperature is 120～180 ℃, working pressure is 1～5MPa, the residence time is 60～240min, in this Diels-Alder reaction process, material is from series connection tubular type reactor head charging bottom discharge,
(3) reaction mixture obtained above enters rectifying tower (T2) after water cooler (E3) is cooling, the tower top service temperature is 0～20 ℃, operating pressure is 0.1～0.3MPa, tower top obtains unreacted 1, turn back to series connection tubular reactor (R2) after the 3-divinyl is freezing front, material by transferpump (P3) extraction at the bottom of tower enters rectifying tower (T3), the tower top service temperature is 30～70 ℃, working pressure is 0.1～0.5MPa, reflux ratio is 0.5～2, tower top obtains unreacted CPD and circulating solvent, and to turn back to series connection tubular reactor (R2) front, obtain crude ethylene basic ring hexene VCH at the bottom of tower,
(4) the thick VCH obtained at the bottom of above-mentioned tower enters rectifying tower (T4), and the tower top service temperature is 30～70 ℃, and working pressure is 0.001～0.005MPa, and reflux ratio is 0.5～3, and tower top obtains refining VCH, obtains mixture at the bottom of tower;
(5) mixture obtained at the bottom of step (4) tower enters rectifying tower (T5), and the tower top service temperature is 30～80 ℃, and working pressure is 0.001～0.005MPa, and reflux ratio is 0.5～3, and tower top obtains VNB, obtains mixture at the bottom of tower;
(6) VNB that step (5) tower top obtains is after molecular sieve drying bed (R6) dehydration, send into isomerization reactor (R7), under the effect of isomerization catalyst, reaction generates thick ENB, the isomerization reaction service temperature is 10～30 ℃, working pressure is 0.01～0.2MPa, and the residence time is 3～7h; The mixture obtained at the bottom of tower enters rectifying tower (T6), and the tower top service temperature is at 40～90 ℃, and working pressure is 0.001～0.005MPa, reflux ratio 0.5～3, and tower top obtains tetrahydroindene THI, obtains the DCPD fraction at the bottom of tower;
(7) thick ENB step (6) obtained enters ENB rectifying tower (T7), operating pressure is 0.001～0.01MPa, the tower top service temperature is 50～60 ℃, the side line service temperature is 60～80 ℃, the tower reactor service temperature is 70～90 ℃, side line obtains highly purified ENB, obtains light constituent at the bottom of tower, obtains heavy constituent at the bottom of tower.
2. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, is characterized in that: the high-purity C PD mass content in described step (1) >=99%; The depolymerization temperature is 220～250 ℃, and operating pressure is 0.05～0.1Mpa; Tower top temperature is 40～50 ℃, and the tower reactor temperature is 140～160 ℃, and reflux ratio is 2～4.
3. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, is characterized in that: before the middle high-purity C PD of described step (2) mixes with circulating solvent, polymerization retarder, adopt refrigerated water to carry out cold insulation.
4. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: the circulating solvent in described step (2) is methylcyclopentane, octane-iso, 6# solvent oil, THF, heptane, methyl ethyl ester or vinyl acetic monomer; Polymerization retarder is compound inhibitor, and by 2,6 di t butyl phenol, 2,6-di-tertiary butyl methyl phenol and naphthyl alcohol 2:1:1 in mass ratio are composited.
5. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: the Diels-Alder reaction service temperature in described step (2) is 120～140 ℃, working pressure is 3～5MPa, and the residence time is 180～240min.
6. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: rectifying tower (T2) the tower top service temperature in described step (3) is 10～20 ℃, and working pressure is 0.2～0.3MPa; Rectifying tower (T3) tower top service temperature is 40～60 ℃, and working pressure is 0.1～0.2MPa, and reflux ratio is 1～2.
7. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: rectifying tower (T4) the tower top service temperature in described step (4) is 40～60 ℃, and working pressure is 0.003～0.005MPa, and reflux ratio is 1～2; Rectifying tower (T5) tower top service temperature in described step (5) is 50～70 ℃, and working pressure is 0.003～0.005MPa, and reflux ratio is 1～2.
8. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, is characterized in that: the super basic catalyst (Na that the isomerization catalyst in described step (6) is pH>=43
2o-NaOH)/AL
2o
3; The isomerization reaction service temperature is 20～30 ℃, and working pressure is 0.05～0.1MPa, and the residence time is 5～6h; Rectifying tower (T6) tower top service temperature is 50～70 ℃, and working pressure is 0.003～0.005MPa.
9. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: ENB rectifying tower (T7) operating pressure in described step (7) is 0.003～0.005MPa; The purity of side line extraction ENB >=99%.
10. the preparation method of a kind of high purity ethylidene norbornene according to claim 1, it is characterized in that: the ENB light constituent that the THI that the VCH that described step (4) obtains and step (6) obtain, step (7) obtain is at BF
3effect under, at-20～120 ℃ of polymerization reaction take places, generate copolymerized petroleum resin with sylvic oil, the main component of this copolymerized petroleum resin comprises Vinyl toluene, indenes and first indenes; The ENB heavy constituent that the DCPD cut that the depolymerization stillage residue that described step (1) obtains and step (6) obtain, step (7) obtain is carried out heat polymerization under 200～300 ℃, generates the hot polymerization petroleum resin.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098423A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Production method for ENB (5-ethylene-2-norbornylene) |
| CN104098422A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Method for isomerizing 5-vinyl-2-norbornylene to produce 5-ethylene-2-norbornylene |
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| CN105175634A (en) * | 2015-09-30 | 2015-12-23 | 宁波职业技术学院 | Preparation method of modified C5 petroleum resin |
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| CN105461505A (en) * | 2015-12-07 | 2016-04-06 | 上海派尔科化工材料股份有限公司 | Production method of ENB (ethylidene norbornene) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4826748A (en) * | 1971-08-07 | 1973-04-09 | ||
| CN1218449A (en) * | 1996-03-13 | 1999-06-02 | 奥普塔技术公司 | Method for preparing norbornene and substituted derivatives of norbornene |
| CN1377869A (en) * | 2001-03-28 | 2002-11-06 | 住友化学工业株式会社 | Process for producing purified dicyclic amylic diene and 5-sub ethyl-2-norbornene |
| CN102010285A (en) * | 2010-11-02 | 2011-04-13 | 宁波职业技术学院 | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions |
| CN102516010A (en) * | 2011-11-25 | 2012-06-27 | 大庆华科股份有限公司 | Method and equipment for separating diolefin component in oil cracking ethylene byproduct carbon-5 fraction |
-
2013
- 2013-09-02 CN CN201310393790.XA patent/CN103483135B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4826748A (en) * | 1971-08-07 | 1973-04-09 | ||
| CN1218449A (en) * | 1996-03-13 | 1999-06-02 | 奥普塔技术公司 | Method for preparing norbornene and substituted derivatives of norbornene |
| CN1377869A (en) * | 2001-03-28 | 2002-11-06 | 住友化学工业株式会社 | Process for producing purified dicyclic amylic diene and 5-sub ethyl-2-norbornene |
| CN102010285A (en) * | 2010-11-02 | 2011-04-13 | 宁波职业技术学院 | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions |
| CN102516010A (en) * | 2011-11-25 | 2012-06-27 | 大庆华科股份有限公司 | Method and equipment for separating diolefin component in oil cracking ethylene byproduct carbon-5 fraction |
Non-Patent Citations (1)
| Title |
|---|
| 杨连玺，: ""乙叉降冰片烯的制备及性质"", 《合成橡胶工业》, vol. 3, no. 4, 1980, pages 249 - 253 * |
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| CN104098423A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Production method for ENB (5-ethylene-2-norbornylene) |
| CN104098423B (en) * | 2014-07-25 | 2016-08-17 | 中石化上海工程有限公司 | The production method of 5-ethylidene-2-norbornene ENB |
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| CN104692994A (en) * | 2015-02-13 | 2015-06-10 | 浙江大学 | Method of synthesizing ethylidene norbornene by virtue of microchannel reactor |
| CN105254808A (en) * | 2015-09-30 | 2016-01-20 | 宁波职业技术学院 | Method for preparing modified petroleum resin |
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| CN105461505B (en) * | 2015-12-07 | 2017-12-19 | 上海派尔科化工材料股份有限公司 | A kind of production method of ethylidene norbornene |
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